Water dispersible thickeners comprising hydrophilic polymers coated with particulate fatty acids or the salts thereof

Abstract: The present invention provides a water dispersible particulate polymer composition having improved water dispersibility comprising a water soluble particulate polymer which has been contacted with a finely divided particulate dispersant comprised of at least one insoluble or sparingly soluble fatty acid or salt thereof so that the particles of the water soluble particulate polymer have dispersed thereon said finely divided particulate dispersant, a method for making said water soluble particulate polymer composition, and the use thereof in viscosifying water-based fluids.

Description: Field of the Invention The invention relates to a composition and process for providing water-soluble polymers with improved dispersibility in water. Background of the Invention Water-soluble high molecular weight polymers are conventionally utilized in the form of dilute aqueous solutions. Although the polymers as manufactured can be dispersed in water to provide homogeneous solutions, care must be exercised in achieving an initial dispersion of the polymer in water. Unless proper precautions are taken, the polymer is likely to agglomerate upon wetting with water to form partially hydrated agglomerated polymer which is slow to dissolve. Moreover, the agglomerated polymer has a tendency to plug liquid handling equipment. Although complete dissolution of the agglomerated polymer is possible, its achievement may require extended periods of time or special treatments to promote rapid dissolution of the gels. Removal of the agglomerated polymer from solutions is also an alternative but is wasteful of polymer. A nonclumping, delayed action viscosity increasing agent comprising core particles of xanthan gum and an encapsulating coating of a fat derivative selected from fatty acids and mono-/diglycerides of fatty acids and a surfactant are known from US patent 4,218,262. US patent 4,720,303 describes a thickening agent which comprises a cellulose ether and a solid acid. EP-A 0 565 354 describes a pesticidal composition allowing the continuous production of high quality tables which exhibit improved disintegrability and dispersibility in water. Such composition comprises, apart from a pesticidal agent, at least one surface active agent; one carbonate; one solid acid; one of talc, calcium stearate, magnesium stearate and titanium dioxide; and one of low-substituted hydroxy propyl cellulose, carboxymethyl cellulose, calcium carboxymethyl cellulose, and crosslinked sodium carboxymethyl cellulose or carboxymethyl starch. Thus, a process for readily dispersing high molecular weight polymers would represent a significant contribution to the art. Summary of the Invention It is thus an object of this invention to provide a novel polymer composition which is more easily dispersed in water-based fluids. It is a further object of this invention to provide a method of making a novel polymer composition which is more easily dispersed in water-based fluids. It is a still further object of this invention to provide a method for improving the dispersibility of water-soluble particulate polymers upon combining with water-based fluids. Other aspects and objects of this invention will become apparent hereinafter as the invention is more fully described. In accordance with the present invention, a water-dispersible particulate polymer composition has been discovered, the composition having improved water dispersibility and consisting of a water-soluble particulate polymer contacted with a finely divided particulate dispersant comprised of at least one fatty acid or salt thereof, which is sparingly soluble or insoluble in water, so that the particles of the water-soluble particulate polymer have dispersed thereon said finely divided particulate dispersant, which is defined to possess a solubility in water of not more than 0.3 g/ℓ (at 20°C) and a melting point of at least 50°C. In accordance with another aspect of this invention, a method for making a water-dispersible particulate polymer composition possessing improved dispersibility characteristics has been discovered, the method comprising the step of contacting a water-soluble particulate polymer with a finely divided particulate dispersant comprised of at least one fatty acid or salt thereof, which is insoluble or sparingly soluble in water, in an amount effective to improve the water dispersibility of the water soluble polymer, so that the particles of the water soluble particulate polymer have dispersed thereon the finely divided particulate. In accordance with still another aspect of this invention, it has been discovered that the process of dispersing water-soluble polymers in water-based fluids can be improved by using the water-dispersible particulate polymer composition described above. Detailed Description of the Invention Water-soluble particulate polymers which are suitable for use in the invention are well known in the art. The water-soluble particulate polymer should be in a dry solid state and in general have a particle size with a diameter in the range of 1 to 1,000 microns. Such water-soluble polymers are selected from cellulose ethers, starches, gums, biopolysaccharides, and synthetic water-soluble polymers. Examples of suitable cellulose ethers are those selected from carboxymethylcellulose, methylcellulose, carboxymethylhydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, and hydroxyethylcellulose. Examples of suitable starches include those selected from carboxymethylstarch, hydroxyethylstarch, and hydroxypropylstarch. Examples of suitable gums are those selected from arabic, trajacanth, karaya, shatti, locust bean, guar, psyllium seed, quince seed, agar, algin, carrageenin, furcellaran, pectin, gelatin, and larch gum. The biopolymers useful in this invention are biopolymers produced by a process comprising the microbial transformation of a carbohydrate with a microorganism to obtain a polymeric material which differs from the parent polymeric material in respect of composition, properties and structure. Suitable carbohydrates include sugars such as pentoses or hexoses, for example glucose, sucrose, fructose, maltose, lactose, galactose, and starches, for example soluble starch or corn starch. Crude products having a high carbohydrate concentration can be used. Among suitable materials there may be mentioned raw sugar or crude molasses. Microorganisms suitable for effecting the microbial transformation of the carbohydrates may be for example plant pathogenic bacteria such as plant pathogens, which produce exsudates on the site of lesions on infected plants. Typical of such microorganisms are the species of the genus Xanthomonas. Thus, for example a heteropolysaccharide biopolymer may be prepared from glucose by the action of Xanthomonas campestris (XC polymer). Commercially available xanthan gum biopolymers can be obtained from Kelco Div., Merck & Col. Inc. under the trademark of "Kelzan", and from General Mills, Inc. under the trademark "Biopolymer XB23". Other species of Xanthomonas bacteria which are useful in preparing the biopolymers include Xanthomonas phaseoli , Xanthomonas mulvacearn, Xanthomonas carotae , Xanthomonas translucens, Xanthomonas hederae, and Xanthomonas papavericoli . Other biopolymers, so-called synthetic gums, which are useful in this invention include: gum dextran synthesized by the action of the bacterium known as genus Leuconostoc Van Tieghement on sucrose, as described by Bailey et al. in U.S. Pat. No. 2,360,237; phosphorylated mannan synthesized by the action of the yeast Hansenula holstii NRRL-Y2448 on glucose as disclosed in U.S. Dept. of Agriculture, Agricultural Research Service, Northern Utilization Research and Development Division, Peoria, Ill., Bulletin CA-N-7, October 1958; gums produced by the action of diphtheriodic bacteria such as Arthrobacter viscous NRRL B-1973 and Arthrobacter viscous NRRL B-1797 as disclosed in Cadmus et al. in U.S. Pat. No. 3,228,855; gum produced by the action of Methylomonas mucosa as described in Finn et al. in U.S. Pat. No. 3,923,782; gum produced by the action of Erwinia tahitica as disclosed in Kang et al. in U.S. Pat. No. 3,933,788; and gum produced by the action of Azotobacter indicus variety Myxogenes as disclosed in Kang et al. in U.S. Pat. No. 3,960,832. Examples of suitable biopolysaccharides include those selected from polysaccharides produced by the action of Xanthomonas campestris, Xanthomonas phaseoli, Xanthomonas mulvacearn, Xanthomonas carotae, Xanthomonas translucens , Xanthomonas hederae, Xanthomonas papavericoli, Hansenula holstii , Arthrobacter viscous, Methylomonas mucosa, Erwinia tahitica, and Azotobacter indicus. As used in this application, the term synthetic water-soluble polymer refers to those synthesized polymers which are truly water-soluble or which are dispersible in water or other aqueous media to form a stable colloidal suspension. Examples of suitable synthetic water-soluble polymers are homopolymers, copolymers, terpolymers, and polymers prepared from more than three monomeric components, wherein the synthetic water-soluble polymer is prepared from one or more monomers selected from acrylic acid and the alkali salts thereof, methacrylic acid, the alkali salts thereof, acrylamide, methacrylamide, acrylonitrile, N-vinyl-2-pyrrolidone, 2-acrylamido-2-methylpropane sulfonic acid, the alkali salts thereof, vinyl alcohol, maleic acid, maleic anhydride and itaconic acid, or polymers containing equivalent functional units. More preferred water-soluble polymers are those prepared from one or more monomers selected from acrylic acid, the alkali salts thereof, acrylamide, N-vinyl-2-pyrrolidone, 2-acrylamido-2-methylpropane sulfonic acid, the alkali salts thereof, and polymers containing equivalent functional units. Preferred copolymers are those prepared from monomeric components consisting of acrylic acid and acrylamide, acrylic acid and acrylonitrile, acrylic acid and methacrylonitrile, acrylic acid and N-vinyl-2-pyrrolidone, acrylamide and N-vinyl-2-pyrrolidone, acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate, or acrylamide and 2-acrylamido-2-methylpropane sulfonic acid or copolymers containing equivalent functional units as the preceding copolymers. Preferred terpolymers are those prepared from monomeric components consisting of sodium acrylate, acrylamide, and sodium 2-acrylamido-2-methylpropane sulfonate; sodium acrylate, N-vinyl-2-pyrrolidone, and sodium 2-acrylamido-2-methylpropane; or of acrylamide, N-vinyl-2-pyrrolidone, and sodium 2-acrylamido-2-methylpropane sulfonate or terpolymers containing equivalent functional units. For the purpose of this invention, it is contemplated that methacrylic acid or its alkali salts may be substituted for acrylic acid, and methacrylamide may be substituted for acrylamide as equivalent monomers. Preferred synthetic polymers prepared from more than three monomeric components are those, wherein the monomeric components are selected from acrylamide, acrylic acid, N-vinyl-2-pyrrolidone, and 2-acrylamido-2-methylpropane sulfonic acid, or polymers containing equivalent functional units. Procedures for making the preceding polymers from the designated monomeric compositions are readily available to one skilled in the art. The procedures discussed in U.S. Patent 5,080,809 are specifically cited. For the purposes of this invention, the terminology "polymer-containing equivalent functional units" is defined to be those polymers which are not prepared from the identified monomeric compositions, but which have been chemically modified following polymerization to give a polymer containing the same functional units attached to the polymer backbone. An example is the saponification (i.e., hydrolysis) of some of the amide functional groups in acrylamide polymers to carboxylate functional units, thereby resulting in a polymer with the same functional units (i.e., amide and carboxylate) attached to the polymer backbone as exist for copolymers prepared from acrylamide and acrylate salt monomers. Additionally for the purposes of this invention, polymers containing acidic functional units are viewed as interchangeable and equivalent to the alkali salts thereof (i.e., acrylic acid may be interchanged with potassium acrylate, sodium acrylate, or ammonium acrylate salts) wherein the alkali salts are potassium salts, sodium salts, and ammonium salts. The above identified polymers may also contain de minimis amounts of water-insoluble monomers, provided the resultant polymer remains water-soluble. The use of mixtures of the above identified synthetic water-soluble polymers is also within the scope of this invention. The finely divided particulate dispersant, which is contacted with the water-soluble polymer, is generally comprised of at least one fatty acid or salt thereof, which is generally hydrophobic in nature, that is sparingly soluble or insoluble in water and exists in particulate form, as long as the particulate dispersant possesses a solubility in water of less than 0.3 g/ℓ at 20°C and a melting point of 50°C or more. Fatty acids as used herein refers to carboxylic acids containing 6 to 24 carbon atoms. These acids may contain different degrees of saturation and include, but are not limited to straight chain alkanoic acids, straight chain alkenic acids, acetylenic fatty acids, polyunsaturated fatty acids, and cyclic carboxylic acids. Fatty acids are generally derived from natural fats and oils such as animal tallows and grease, and vegetable, coconut, palm, and marine oils. Preferred are fatty acids and salts thereof, which are comprised of alkanoic acids and the Group IA, Group IIA, Group IIB, Group IIIA, Group VIIB, or the Transition Metal salts thereof, which meet the preceding solubility and melting point criteria and contain at least 10 carbon atoms. For these fatty acid salts, salts possessing a cation selected from sodium, magnesium, calcium, barium, zinc, cadmium, nickel, manganese, copper, and aluminum are preferred. Stearic acid and the associated salts thereof are still more preferred. Preferred stearic acid salts are those possessing a cation selected from sodium, magnesium, calcium, zinc, nickel, manganese, copper, and aluminum. More preferred stearic acid salts are selected from sodium stearate, calcium stearate, and magnesium stearate. Although the performance characteristics for sodium stearate were not as good as some of the other stearate salts, the sodium cation may be preferred in certain systems over the heavier cations which, among other things, may complex with other species. For the practice of this invention, the most preferred fatty acid is stearic acid and the most preferred fatty acid salt is calcium stearate. Because of cost, commercial availability and performance characteristics, the most preferred particulate dispersant is calcium stearate. The finely divided particulates should have a particulate size ranging from 0.0001 microns to 250 microns and most preferably range from 0.0001 microns to 150 microns. Suitable techniques for making the finely divided particulate dispersants are known to those skilled in the art. The uncompacted bulk density of the finely divided particulate dispersant should range from 0.10 g/mℓ to 0.60 g/mℓ, and preferably range from 0.20 g/mℓ to 0.40 g/mℓ. The bulk density was determined by sifting the material into a 10 mℓ graduated cylinder (without shaking). The cylinder was then gently shaken for about 5 seconds to level the surface of the material. The total volume and the total weight of the material in the cylinder was determined and the uncompacted bulk density was calculated by the following formula: Uncompacted bulk density = Weight Volume . The water-soluble particulate polymer and the finely divided particulate dispersant should be blended together in a manner which facilitates the thorough mixing of water-soluble polymer particles with the finely divided particulate; preferably a substantially homogeneous mixture of the particulate components will be formed. Theoretically, the thorough mixing of these two particulate components is thought to distribute the finely divided particulate dispersant over the surface of the larger water-soluble polymer particles. Currently, it is preferred to dry-blend the water-soluble polymer with the finely divided polymer by dry-mixing in a blender. The amount of finely divided particulate dispersant in the final dry composition comprising dispersant and water-soluble polymer should be an amount effective to improve the dispersibility of the water-soluble polymer upon combining with a water-based fluid. Preferably, the dispersant in the final composition should be in the range of 0.1 weight percent to 30 weight percent, more preferably in the range of 1 weight percent to 30 weight percent, and still more preferably 2 weight percent to 20 weight percent, based on the total weight percentage of the water-soluble particulate polymer and finely divided particulate dispersant totalling 100 weight percent. The dispersing of the water-dispersible particulate polymer composition into a water-based fluid can be conducted using any of the means available to one skilled in the art; the inventive feature of this process resides in the improvement in rate and ease of dispersion, when the water-soluble polymer is first made part of the water-dispersible particulate polymer composition herein described. The following nonlimiting examples are provided to further illustrate this invention. Example I A quantitative demonstration of the enhanced water solubilization characteristics of particulate carboxymethylcellulose contacted with either finely divided aluminum stearate or magnesium stearate dispersant over uncontacted carboxymethylcellulose is presented in Table I. Dispersant particle size distribution data is presented in Table II for several candidate dispersants. Uncompacted bulk densities for these candidates are presented in the footnotes to Table II. Blends of carboxymethylcellulose and the finely divided dispersants were prepared by combining in small vials 9.8 g polymer with 0.2 g dispersant and shaking the mixture by hand for approximately two minutes (i.e., until the particles were homogeneously distributed). The tests were conducted by respectively dumping 0.64 g samples of uncoated carboxymethylcellulose (sample A), a 2/98 wt/wt blend of aluminum stearate/carboxymethylcellulose (inventive sample B), and a 2/98 wt/wt blend of magnesium stearate/carboxymethylcellulose (inventive sample C) into separate Kerr pint jars containing 280 ml tap water, whereupon each mixture was immediately stirred with a multimixer for one minute and then immediately transferred to a Fann VG viscometer (Model 35A) for viscosity measurements as a function of time. By definition, the apparent viscosity in centipoise is 50% of the reported measurement value. The results are presented in Table I. All tests were conducted at room temperature. Effects of Particulate Dispersants on the Solubilization of Carboxymethylcellulose Elapsed Time After Mixing (Min.) Particulate Dispersant None Al Stearate Mg Stearate 1 5 cp 25 cp 15 cp 3 5 27 17 5 7 30 20 7 7 30 21 10 8 30 22 15 9 30 24 20 10 30 25 25 10 30 26 30 10 30 27 40 12 30 27 50 13 30 27 60 14 30 27 70 16 29 27 The results presented in Table I demonstrate the beneficial effects on the solubilization of a water-soluble polymer when a properly selected particulate dispersant is intermixed with the polymer. The viscosity of the sample which contained no dispersant (Sample A) gradually increased from a one minute value of 5 to a value of only 16 after more than an hour. In contrast, the sample containing aluminum stearate as e dispersant (inventive sample B) had a one minute value of 25 and quickly plateaued at a value of 30 after only 5 minutes, thereby indicating rapid solubilization of the water-soluble polymer. The sample containing magnesium stearate as a dispersant (inventive sample C) had a one minute value of 15 which was three times greater than the corresponding value for sample A and plateaued at an apparent maximum of 27 after only 30 minutes indicating rapid solubilization of the water soluble polymer. Particle Size Distribution Using Ro-Tap Sieve Shaker (Five Minute Shake Time) Tyler Mesh Sizes Dispersant +100 -100 to +200 -200 to +325 -325 Aluminum Stearate 5.8 wt% 80.7 wt% 11.9 wt% 1.6 wt% Magnesium Stearate 2.7 86.8 9.8 0.7 Stearic Acid (ground) 60.3 25.2 14.3 0.2 Magnesium Oxide 1.5 81.2 10.6 6.7 Calcium Stearate 2.8 70.1 24.2 2.9 Example II Qualitative studies of prospective particulate dispersants were conducted by combining the candidate dispersants with a water-soluble polymer (carboxymethylcellulose) using the procedure given in Example 1. Test solutions were then prepared by dumping 0.64 g of the sample of interest into a Kerr pint jar containing 280 mℓ of tap water. Particle size distribution for several of the dispersants has been previously presented in Table II. Upon dumping the sample into the Kerr pint jar, the solution was immediately stirred for one minute in a multimixer whereupon observations of sample dispersibility were made and are reported in Table III. All tests were conducted at room temperature. Qualitative Performance of Candidate Water-Soluble Particulate Dispersing Agents Dispersant Observation None Large polymer clumps Calcium Stearate Mostly dispersed, some small clumps Aluminum Stearate Mostly dispersed, some small clumps Magnesium Stearate Mostly dispersed, some small clumps Sodium Stearate c Small clumps, few medium large clumps Stearic Acid Some small clumps, one larger clump Hydrophobic Fumed Silica Mostly dispersed, some small clumps Hydrophobic Fumed Silica Mostly dispersed, some small clumps Fumed Silica Large polymer clumps Magnesium Oxide Large polymer clumps Kaolin Large polymer clumps Talc Large polymer clumps The results presented in Table III show that candidate particulate dispersants calcium stearate, aluminum stearate, magnesium stearate, sodium stearate, and stearic acid significantly outperform candidate dispersants magnesium oxide, fumed silica, kaolin, and talc for dispersing the water-soluble polymer carboxymethylcellulose in water. The calcium, aluminum, and magnesium stearates exhibited performance characteristics equivalent to the more expensive hydrophobic fumed silicas. Example III This example supplements in a quantitative manner the qualitative results presented in Example II. The test samples and solutions were prepared in an analogous manner (i.e., addition of 0.64 g of sample to 280 ml tap water and then stirred for 1 minute with a multimixer). The solutions were then immediately transferred to a Fann VG viscometer (Model 35A). At the reported times, the viscometer was turned on and viscosity measurements at 600 rpm were obtained. By definition, the measurement readings obtained at 600 rpm and presented in Table IV correspond to the apparent viscosity in centipoise when divided by two. All tests were conducted at room temperature. Quantitative Performance Characteristics of Candidate Particulate Dispersants for Water-Soluble Polymers 600 rpm Reading Dispersant After Five Minutes After One Hour No Dispersant 7 (7) cp 9 (14) cp Calcium Stearate 24 (25) 29 (29) Aluminum Stearate 29 (28) 30 (28) Magnesium Stearate 24 (28) 27 (28) Sodium Stearate c 19 24 Stearic Acid 25 (16) 29 (20) Hydrophobic Fumed Silica 25 29 Hydrophobic Fumed Silica 25 29 Fumed Silica 4 (10) 5 (12) Magnesium Oxide 8 (7) 10 (9) Kaolin 10 11 The results presented in Table IV clearly establish calcium, aluminum, and magnesium stearates to be equivalent in performance to the hydrophobic fumed silicas and markedly superior to the other candidate dispersants. For the aluminum, calcium,and magnesium stearate dispersants, the viscosity reading at 5 min. was 82 to 100% of the one hour reading. This is indicative of excellent dispersing characteristics. The results also indicate sodium stearate and stearic acid to be superior to fumed silica, magnesium oxide, and kaolin. The stearic acid did not perform in all tests as well as aluminum, calcium, or magnesium stearate. However, the stearic acid particles were of larger particle size and improvement in performance is likely possible by using smaller sized particles. The preparation of such particles is readily within the capabilities of one skilled in the art. Additionally, the use of stearic acid at greater weight ratios as a means of increasing the dispersibility of water-solubie polymers may be economically favored under certain situations.

Claims: A water-dispersible particulate polymeric composition consisting of (a) a water-soluble particulate polymer selected from cellulose ethers, gums, starches, synthetic water-soluble polymers and biopolysaccharides, and (b) a finely divided particulate dispersant comprised of at least one water-insoluble or sparingly soluble fatty acid or fatty acid salt, the particulate dispersant being defined to possess a solubility in water of ≤ 0.3 g/l at 20 °C and a melting point of ≥ 50 °C, wherein the finely divided particulate dispersant is distributed over the surface of the water-soluble particulate polymer. The composition of claim 1, wherein said dispersant (b) is present in the range of 0.1 to 30 wt% based on the total of (a) plus (b). The composition of any of the preceding claims, wherein said fatty acid is comprised of an alkanoic acid containing at least 10 carbon atoms and said salts thereof are selected from Group IA, Group IIA, Group IIB, Group IIIA, Group VIIB and the Transition Metal salts. The composition of claim 3, wherein said fatty acid is stearic acid and said salts contain a cation selected from sodium, magnesium, calcium, zinc, nickel, manganese, copper, and aluminum. The composition of claim 4, wherein said cation is selected from sodium, calcium and magnesium. The composition of any of the preceding claims, wherein said dispersant is calcium stearate. The composition of any of the preceding claims, wherein said cellulose ethers are selected from carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, and carboxymethylhydroxyethylcellulose; said starches are selected from carboxymethylstarch, hydroxyethylstarch, and hydroxypropylstarch; said gums are selected from arabic, trajacanth, karaya, shatti, locust bean, guar, psyllium seed, quince seed, agar, algin, carrageenin, furcellaran, pectin, gelatin and larch gum; said synthetic water-soluble polymers contain one or more monomers selected from acrylic acid, the alkali salts thereof, methacrylic acid, the alkali salts thereof, acrylamide, methacrylamide, acrylonitrile, N-vinyl-2-pyrrolidone, 2-acrylamide-2-methylpropane sulfonic acid, the alkali salts thereof, vinyl alcohol, maleic acid, maleic anhydride, itaconic acid, and equivalent functional monomers; and said biopolysaccharide is selected from polysaccharides produced by the action of Xanthomonas campestris, Xanthomonas phaseoli, Xanthomonas mulvacearn, Xanthomonas carotea, Xanthomonas translucens, Xanthomonas hederae, Xanthomonas papavericoli, Hansenula holstii, Arthrobacter viscous, Methylomonas mucosa, Erwinia tahitica, or Azotobacter indicus. The composition of any of the preceding claims, wherein said polymer (a) is carboxymethylcellulose. The composition of claim 7, wherein said synthetic water-soluble polymer is prepared from one or more monomers selected from acrylic acid, the alkali salts thereof, acrylamide, N-vinyl-2-pyrrolidone, 2-acrylamido-2-methylpropane sulfonic acid, and the alkali salts thereof. The composition of claim 7, wherein said polysaccharide is produced by Xanthomonas campestris. The use of the composition of any of claims 1 to 10 for preparing viscosity-increased water-based fluids. The use of claim 11, wherein said water-based fluids are drilling muds. A method for preparing the composition of any of claims 1 to 10, the method comprising the step of contacting a water-soluble particulate polymer with a finely divided particulate dispersant, wherein both the polymer and the dispersant are as defined in claim 1.

Inventors: PATEL BHARATKUMA BALUBHAIL, PATEL, BHARATKUMA BALUBHAIL
Applicants: PHILLIPS PETROLEUM CO, PHILLIPS PETROLEUM COMPANY
Application year: 1994
Main classification: C08L101
IPC codes: C08L3, C08L101, C08L1, C09K8, C08K5, C08L5, C08J3